Coating compositions containing a tertiary amine and a metallic drier



United States Patent This invention relates to air-drying coatingcompositions and particularly to shortening the time required forair-drying, i.e. the spontaneous conversion or curing of a coating ofpaint or the like, by an oxygendnduced reaotion to a condition in whichthe dried coating is no longer. soluble in ordinary solvent for theoriginal liquid coating composition. Such air-drying, in the instantinvention as in the paint art, is most easily effected by exposing abrushed, sprayed or otherwise applied coating to the atmosphere (oxygen)at normal temperatures of about 40-100 F.

The improvement of shortened air-drying time provided by this inventionis effected by incorporating as an accelerator in the liquid paint orlike material a di(polyoxyethylene). tertiary amine having the followingstructural formula:

in which R is selected from the class consisting of C -C3 alkyl,

i C -C alkenyl and benzyl, and m and n are integers having a total valueof 8 to 16 in elusive.

Polyoxyethylated fatty amines, i.e. fatty primary amines converted totertiary amines by replacing the two amino hydrogen atoms withpo-lyoxyethylene substituents,

represent this class of compound. The fatty amine can be methyl, butyl,octyl, stearyl amine or the like, including coco, soya and tall amine.The last three of these are mixed fatty amines corresponding to themixed fatty acid moieties present in coconut, soya and tall oil.

The Ethomeens C/20, C/25, 8/20, 8/25, T/25, 18/ 20 and 18/25 arepolyoxyethyla-ted coco, soya, tall or stearyl amines containing 10 to 15ethyleneoxy units per molecule and exemplify tertiary amines which areuseful in this invention.

Other species of such tertiary amines includeN,N-bis(hydroxyethyltriethoxy)amino methane N,N bis(hydroxyethylpentaethoxy) amino propane N,Nbis(hydroxyethylheptaethoxy)amino pentane The proportion of such a tertiary amine added as anaccelerator is about 0.1%2%, preferably 0.5 %-1%, based on the weight oforganic film-foaming material present in the composition. 2

Of the above described class of tertiary amine-s, a preferred class isthe polyoxyethylated C amines containing about 10 ethyleneoxy groups permolecule because of their availability, 10W cost and high order ofactivity in accelerating air-drying.

An essential organic film-forming component of the coating compositionsof this invention is a compound containing a plurality of 1,3-cyclicacetal radicals having in the Z-position an alpha-methylenicallyunsaturated substituent. A wide variety of such compounds is disclosedin US. Patents 3,010,918 and 3,010,923, and the compounds of thesepatents are useful as film forming materials in this invention.

A preferred class of such acetal compound for use in this invention ispolycarboxylic acid esters containing a plurality of monovalent2-vinyl-l,3-dioxolanyl radicals, because they dry fast, have excellentcoating properties and are easy and economical to make. The followingcompounds are representative of this preferred class:

Bis (2-vinyl-1,3 -dioxol an-4-yl )butyl] orthophth alate Bis (2-vinyl- 1,3 -diox0l-an-4-yl) butyl] itaconate Bis 2-vinyll 3-d:ioxolan-4-yl)buty1] maleate Bis 2-vinyl-l ,3 -dio-x olan-4-yl butyl]fumarate Bis (2-vinyl-1, 3-dioxolan-4-yl) butyl te rephthalate Bis(2-vinyll 3 -dioxolan-4-yl )butyl] mes acon ate Tetrakis[ (Z-vinyl-l 3-d-ioxolan-4-yl butyl] pyromellitate Tris (2-vinyl-1 3 -dioxolan-4-yl)butyl] propane tricarb oxylate Bis (2-vinyl-1, 3 -dioxolan-4-yl butyl]hexahydro phthal ate B'is[ (2-vinyll 3 -dioxol an-4-yl pnopylcitraconate Tris (2-vinyl-l ,3 -dioxol an-4-yl )propyl1trim ellitate Bis2-vinyl-1 3 -dioxolan-4-yl )propyl] isophthala-te Bis (2-vinyl-1,3-di0xolan-4-yl methyl] maleate Bis (2-vinyl-1,3 -dioxolan-4-yl)methyl1glutarate Bis (Z-Vinyl-l ,3 -dioxol an-4-yl methyl] adipateWithin the above mentioned preferred class a further preferred class isdicarboxylic acid diesters having two monovalent 2-vinyl-l,3-dioxolanylradicals, several representative species of which are set forth above.These are especially preferred because they have the earlier mentionedcharacteristics in a high degree and have a relatively low viscositygenerally like raw linseed oil.

Another kind of compound containing a plurality of acetal groups asdescribed above which is useful as an essential film-former in thisinvention is a linear polymer having such acetal groups as extralinearsubstituents which are pendant from the main polymer chain. Suchpolymers can be prepared for example by transesteri'fying (a) a readilysoluble preformed vinyl addition polymer having extralinear carbalkoxygroups (preferably C -C carbalkoxy groups) attached to different carbonatoms, with (b) a hydroxyalkyl-substituted 1,3-cyclic acetal -having inthe 2-position an alpha-methylenically unsaturated substituent.

A third required component of the coating compositions of this inventionis a siccative metallic drier compound. These compounds are theWell-known siccative metalcontaining compounds or complexes which arecommonly added to drying and semi-drying oil-containing paints,varnishes, enamels and the like to impart air-drying properties theretoor to improve the air-drying prop erties. Suitable metals are, forexample, cobalt, lead, manganese, zinc, iron, nickel, chromium, cerium,calcium, aluminum, titanium, zirconium and magnesium. They are widelyavailable and commonly used in the form of soluble soaps, salts and thelike, such as the chlorides, acetates, hydrates, oxyhydrates, octoates,oleates, linoleates, naphthenates, resinates and alkyl half esters ofdicarboxylic acids (e.g. alkyl phthalate). ldixtures of such com poundscan be used. Cobalt is a preferred metal.

The amount of metallic drier compound used is not critical and varieswidely with the kind of metal, the character of the air-dry ngfilmformer(s) being used, the air-drying speed desired, and the airtemperature.

Metallic drier compounds which are soluble in the composition arepreferred, although it is usually expedient to add the drier as asolution in a common solvent.

Ordinarily the amount of metal drier compound used is equivalent to0.0005%3% of metal (in the drier) based on the total Weight ofair-drying film-forming material. When drying is to occur at normal roomor atmospheric temperature, the amount of metal used is preferably about0.01%1.0%. When force-drying or bak- Paterited Feb. 1, 1966 Q ing isemployed to shorten the drying period, the preferred amount of metalused is preferably 0.0005%0.01%.

Thus the new coating compositions of this invention consist essentiallyof cyclic acetal, di(polyoxyethylene) tertiary amine and drier, each asdescribed hereinbefore.

Although many useful compositions of this invention can be made usingone or more of the above mentioned acetal compounds as the only class ofair-drying filmformer in the composition, other well-known film-formerscan be used in admixture with the essential cyclic acctal component tomodify film and application properties.

Representative kinds of these film-forming additives are the unsaturatedtriglyceride oils such as linseed, soya, China-wood, perilla, dehydratedcastor, saffiower and oiticica oils, oleoresinous varnishes and alkydresins modified with or embodying such oils or the fatty acid moietiesnormally contained in such oils, and mono and poly carboxylic acidesters of dihydropyranyl methanol. For coating compositions of thisinvention which can cure slowly by air-drying and which are normallybaked or force dried at an elevated temperature to hasten the cure, theadditives can also include alkyd resins modified with unsaturated oils(or the corresponding fatty acids) of the so-called non-drying classsuch as castor and coconut oil, epoxy resins such as the condensationproducts of an epihalohydrin and diphenol, amine-aldehyde resins such asalkylated urea formaldehyde and alkylated triazine formaldehyde resins.

A further class of film-forming material which is useful in modifyingthe film and application properties of the coating compositions of thisinvention is mono acetals containing a single 1,3-cyclic acetal radicalhaving in the 2-position an alpha-methylenically unsaturatedsubstituent. Examples of such modifiers are (2-vinyl-1,3-dioxolan 4 ylbutyl)pelargonate, (2-vinyl-1,3-dioxolan-4-ylmethyl)benzoate, and thecorresponding oleates and stearates of each of these.

Other common ingredients of organic coating compositions can be includedin the manner and proportions well-known in the coating ar. Theseinclude solvents and diluents, plasticizers, catalysts, hardeners,surface active agents and the like. Of these, solvent or solvent diluentmixture is the most likely to be neededto reduce the viscosity orconsistency so that it is suitable for easy application, such as byspraying. Suitable solvents and diluents include aliphatic and aromatichydrocarbons, esters, ketones and alcohols, and mixtures thereof.

Conventional pigments and extenders such as metal OX- ides, hydroxides,chromates, silicates, sulfides, sulfates, carbonates, organic dyes andlakes thereof and metalfiake pigments can be used, if desired, in thecoating compositions of this invention in conventional amounts.

The following examples illustrate the principles and practice of thisinvention. It is to be understood that, since only a few representativeembodiments are shown, other embodiments which yield analogous resultscan be easily prepared by substituting for all or part of a component ina specific example an equivalent proportion of a corresponding componentsuggested hereinbefore, with appropriate adjustments if necessary in theproportions or other conditions. Unless otherwise indicated, parts aregiven by weight.

In the examples of coating compositions containing pigment, it is to beunderstood that the pigment is incorporated by any convenient one of theconventional grinding or dispersion methods known to persons skilled inthe coating art. Usually the pigment is worked in a mill with part ofthe film-former until a smooth dispersion having the desired fineness isproduced. Then the balance of the formula is admixed therewith. Sincethis is wellknown, the following examples are not burdened with detailin this connection and show only the ingredients and amounts.Unpigmented (clear) compositions of the example are made by simplyadmixing the specified ingredients.

4; EXAMPLE 1 Brushing primer for steel Parts by wt.Bis[(Z-vinyl-l,3-dioxolan-4-yl)butyl]itaconate 712 2-vinyl- 1 ,3-dioxolan-4-yl-butyl oleate 612 etr-ahydrofurfuryl methacryl-ate 355 43%dehydrated castor oil modified glycerol phthalae alkyd resin solution,unreacted hy- When the accelerator in the above formula is Ethomeen 0/25(polyoxyethylated cocoamine, a tertiary amine containing about 15ethyleneoxy groups per molecule), a brushedout coating dries tack-freein about 4% hours in air at 1 A control (same formula without theaccelerator) tested at the same time requires about 7 hours.

b When the accelerator is Ethomeen 18/20 (polyoxyethylated stearylamine,a tertiary amine containing about 10 ethyleneoxy groups per molecule),the tacktree time is about 4 hours.

These reductions in drying tnne are 35% of the drying time of thecontrol under the same drying conditions.

Reductions of about 10%-l5% are produced in the air-drying time or inthe force drying or baking time of the coating compositions of thefollowing Examples 29 when a tertiary amine set forth hereinbefore isincorporated in the formula in the proportion indicated, and a coatingis applied to an article in the manner indicated by the prescribedutility of the composition. As in Example 1, the degree of improvementis based on the drying time of the corresponding control (withoutaccelerator) EXAMPLE 2 Metal primer for dip application Parts by wt. Bis(2-vinyl-1,3-dioxclan-4-yl) butyl] itaeonate 313(2-vinyl-1,3-dioxol'an-4-yl-butyl)pelargon ate 83 Long oil linseedmodified glycerol phthalate aalkyd resin solution, unreacted hydroxylcontent equivalent to 1.7% glycerin, acid number 5-9, 63% solids in ahydrocarbon solvent having a boiling point of 175233 C. and an anilinepoint of 4 C. 83 Brown iron oxide 347 Zinc chromate 258 Calciumcarbonate Talc 38 Cobalt naphthenate solution (6% cobalt) 5 Accelerator4,

EXAMPLE 3 Enamel for brush or spray application Parts by Wt. Bis[(2-vinyl-1,3-dioxolan-4-yl)butyl] orthophthalate 580 Bis(2-vinyl-1,3-dioxolan-4-yl)butyl]itaconate 200' Titanium dioxide Ferriteyellow 63 Phthalocyanine green 50 Cobalt Octoate solution (8% cobalt) 10Accelerator EXAMPLE 4 Enamel for brush or spray application Parts by wt.Bis[(2-vinyl-l,3-dioxolan-4-yllbutyl]sebacate 480 Bis(2-vinyl-1,3-dioxolan-4-yl)butyl] italconate 160 Titanium dioxide 356Cobalt butyl phthalate (8% cobalt) 8 Accelerator 7 EXAMPLE 5 Clearvarnish for brushing on wood Parts by wt.Bis[(2-vinyl-l,3-dioxolan-4-yl)butyl]fiumarate 1000 Bis[(2-Vxl1'1Yfl-1,3dl0XOlflll-4-Y1)flflltyl] itaconate 2000 Ester gum 1000Mineral spirits 3000 Cobalt octoate solution (8% cobalt) u 37Accelerator 40 EXAMPLE 6 Aerosol self-spraying enamel in pressurizedcontainer Parts by wt. Bis[ (2-vinyl-1,3-dioxolan-4-yl)butyl]orthophthalate 252 Bis (Z- vinyl-l ,3-dioxolan-4-yl )butyl] itaconate252 Titanium dioxide 389 Toluene 33 Acetone 60 Cobalt buty-l phthalatesolution (8% cobalt) 9 Benzoyl peroxide 5 C01 propellent 500 CCl F-propellant 500 Accelerator 5 EXAMPLE 7 Enamel for spray applicationParts by wt. Bis[(Z-vinyl-1,3-dioXolan-4-yl)buty-l]itacon ate 252 Cyclicacetal polymer solution 1 720 Titanium dioxide 389 Cobalt o'ctoatesolution (8% cobalt) 0.5 Accelerator 5 solution in xylene, 55:45styrene:ethyl acrylate preformed polymer solution with ethyl radicalsreplaced via transesterification witha-hydroxybutyl-2-vinyl-1,3-diox0lane. Polymer contains 33.8% by weightof (2-vinyl-1,3-di0x0lan- 4-yl)butyl moiety.

EXAMPLE 8 Baking metal primer for dip application Parts by Wt.Bis[(2-vinyl-l,3-dioxolan-4-yl)butyl]itaconate 105(Z-vinyl-1,3-dioxolan-4-yl butyl)oleate 88 Epoxide resin, Epon 828 1 19Urea-formaldehyde resin, Uformite F240N 2 92 Zinc oxide, zincchro-rrrate 80 Inert fillers 264 Carbon black 38 43% dehydrated castoroil modified glycerol phthalate alkyl resin solution, unreacted hydroxylcontent equivalent to 5% glycerine, acid number 7-13, 56% solids inxylene 119 1 A resin having the formula Parts by wt. Cobalt ootoatesolution (6% cobalt) 1 Accelerator 3 (Baking schedule, 30 minutes at 275F.).

EXAMPLE 9 Black baking enamel for spray application Parts by wt.

Bis[(2-vinyl-1,3-dioxolan-4-yl)buty1]maleate 37% coconut oil modifiedglycerol phthalate alkyd resin solution, vunreacted hydroxyl contentequivalent to 5.4% glycerin, 60% solids in xylol, acid number 4-8 1000Butyl ether of urea-formaldehyde condensate,

50% solids in butanol 600 Carbon black 50 Cobalt octoate solution (6%cobalt) 6.7 Accelerator 10 (Baking schedule, 20 minutes at 325 F.)

I claim:

1. An air-drying liquid coating composition consisting essentially of(a) a compound containing a plurality of 1,3cyclic acetal radicalsconnected through an interposed polyvalent nadical, said cyclic acetalradicals having in the 2position substituents selected from the groupconsisting of vinyl and is-opropenyl, and

(b) a siccative metallic drier compound, and

(c) a di(polyoxyethylene) tertiary amine having the following structuralformula:

(CH CH O)mH RN/ (OH2-CH2O)nH in which R is selected from the classconsisting of (l -C allryl, C -C alkenyl and =bcnzyl, and m and n areintegers having a total value of 8 to 16 inclusive.

2. A composition of claim 1 in which the tertiary amine of (c) is apolyoxyethylated C amine containing about 10 ethyleneoxy groups permolecule.

3. A composition of claim 1 in which the tertiary amine of (c) ispolyoxyethylated coco amine containing about 15 ethyleneoxy groups permolecule.

4. A composition or claim 1 in which the tertiary amine of (c) ispolyoxyethylated :stearyl amine containing about 10 ethyleneoxy groupsper molecule.

5. A composition of claim 1 in which the compound of (a) is apolyoanboxylic acid ester having a plurality of monovalent2-viny1-1,3-dioxolanyl radicals.

6. A composition of claim 1 in which the compound of (a) is adicarboxylic acid diester having two monoval'ent 2-vinyl-1,3-dioxol anylradicals.

7. A composition of claim 1 in which the compound of (a) isbis[(Z-Vinyl-l,3-dioxo1an-4-yl) butyl] orthophthalate.

8. A composition of claim 1 in which the compound of (a) isbis[(2-vinyl-1,3-dioxolan-4-yl)butyl] itaconate.

'9. A composition of claim 1 in which the siccative metallic driercompound of (b) is a cobalt compound.

10. A composition of claim 1 further containing (d) an air-dryingfilm-forming material selected from the The resin has a Gardner-Holdtviscosity of polses maximum and an epoxide equivalent of -210.

2 A urea-formaldehyde resin. It is a 60% solution in high flash naphtha,has a Gardner-Holdt viscosity, of Z2-Z6 and an acid number of 38.

class consisting of unsaturated triglyceride oils, varnishes and alkydresins modified therewith, and monooarboxylic fatty acid esterscontaining the 2viny1-1,3-dioxolanyl radical.

7 11. A method for shortening the air-drying time of a coatingcomposition consisting essentially of (a) a compound containing aplurality of 1,3-cyclic acetal radicals connected through an intenposedpolyvalent nadical, said cyclic acetal radicals having in the 2-positionsubstituents selected from the group consisting of vinyl andisopropenyl, and (b) a siccative metallic dried compound, said methodcomprising air-drying said composition in the presence of an aminehaving the following structural formula:

(CHPCHPOMH (CHgCH1O)nH in which R is selected from the class consistingof C C alkyl, (l -C alkenyl and benzyl, and m and n are integers havinga total value of 8 to 16 inclusive. 12. A method for shortening theair-drying time of a coating composition consisting essentially of (a) acompound containing a plurality of 1,3-cyclic acetal radicals connectedthrough an interposed polyvale-nt radical, said cyclic acetal radicalshaving in the 2-position substituents selected from the group consistingof vinyl and isopropenyl, and

8 (b) a siccative metallic drier compound, said method comprisingincorporating into said composition, before it is air dried, an aminehaving the following structural formula:

5 (OHz-OH2O)mH (CHg-CH -OMH in which R is selected from the classconsisting of C -C lalkyl, C2-C18 alkenyl and 'benzyl, and m and n areintegers having a total value of 8 to 16 inclusive.

LEON J. BERCOVITZ, Primary Examiner.

JAMES A. SEIDLECK, Examiner.

1. AN AIR-DRYING LIQUID COATING COMPOSITION CONSISTING ESSENTIALLY OF(A) A COMPOUND CONTAINING A PLURALITY OF 1,3-CYCLIC ACETAL RADICALSCONNECTED THROUGH AN INTERPOSED POLYVALENT RADICAL, SAID CYCLIC ACETALRADICALS HAVING IN THE 2-POSITION SUBSTITUENTS SELECTED FROM THE GROUPCONSISTING OF VINYL AND ISOPROPENYL, AND (B) A SICCATIVE METALLIC DRIERCOMPOUND, AND (C) A DI(POLYOXYETHYLENE) TERTIARY AMINE HAVING THEFOLLOWING STRUCTURAL FORMULA: